Thiourea-Catalyzed, Hypervalent Iodine-Assisted Deoxygenative or Desulfurative Amidation of Alcohols.

Hydroxyl groups are ubiquitous in natural products and pharmaceuticals. The dehydroxyamidation of alcohols via the Ritter reaction offers a valuable route to amide compounds but faces limited substrate scope due to its reliance on acid-catalyzed carbocation formation. Herein, we report a cooperative thiourea/(bis(trifluoroacetoxy)iodo)benzene catalytic system for the deoxygenative amidation of diverse alcohols under mild conditions. This method exhibits broad substrate compatibility and excellent functional group tolerance, enabling the challenging dehydroxylation of secondary OH groups in saccharides while preserving the acid-sensitive anomeric C(1)-O bond. The utility of this strategy is demonstrated by the direct, one-step synthesis of a rare ribosamine derivative bearing a chiral methyl group at the C5″ position from commercially available rhamnose, achieving excellent stereo- and chemoselectivity.